Process for the polymerization of vinyl chloride

ABSTRACT

In a process for the aqueous suspension polymerization of vinyl chloride, alone or in mixture with other monomers, in the presence of at least one of dialkylperoxydicarbonate, peroxyester and diacyl peroxide, the polymerization composition according to the invention comprises at least one dialkylhydroxylamine as a shortstopping agent along with a totally or partially hindered phenolic antioxidant.

The invention relates to an aqueous suspension polymerization processfor producing polymeric, esp., polyvinyl chloride (PVC) and co-polymersof PVC and PVDF, products with improved color, the process utilizingcombinations of an N substituted hydroxylamine shortstopper with certaintotally or partially hindered phenolic antioxidants.

In the manufacture of polyvinyl chloride, it is important commerciallyto obtain the best yield and quality at the lowest cost. The cost andperformance of the peroxide initiators, shortstopping agent andantioxidant, if used, can be significant factors. Ideally, PVC should beproduced with effective, cheap, non-toxic, shortstopper. There are manyshortstopper to choose from but those based on hydroxylamines may leadto yellowing of the PVC resin. This is particularly true if certainperoxide radicals used in the polymerization process are high enough inenergy to abstract a hydrogen atom from the PVC backbone leading todehydrochlorination.

Di 2-ethylhexylperoxydicarbonate and di(sec-butyl)peroxydicarbonate aretwo common and inexpensive initiators which work well but produce PVCwith poor color.

The most commonly used short-stoppers for the aqueous suspensionpolymerization of vinyl chloride are ATSC (acetone thiosemicarbazone),bisphenol A, sodium nitrite, alpha methyl styrene, butylatedhydroxyanisole, Irganox® 245 (2,4-dimethyl6-sec-hexadecylphenol), aloneor as a mixture with Irganox 1076 [octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] anddiethylhydroxylamine.

Irganox® 1141 (hereinafter IGX 1141) is a commercial mixture of 80 partsby weight of Irganox® 245 and of 20 parts by weight of Irganox® 1076.

However these shortstoppers all have some drawback: poor watersolubility, slow to stop polymerization, toxicity/handling issues.

N,N-diethylhydroxylamine (DEHA), a representative substitutedhydroxylamine compound, has been used in PVC production as a vinylchloride stabilizer, as a “killer” to stop runaway reactions, as anantiscalant, and when added prior to initiation at low levels, to modifyPVC density (sometimes referred to as “stunning” the initiator) or toprevent unwanted polymerization during the induction period.

Hydroxylamine compounds are also known in the industry as PVCshortstoppers; however, most tests indicated that DEHA caused yellowingof the polymer.

U.S. Pat. No. 3,222,334, (Dec. 7, 1965) discloses in the specificationthat N,N-dialkylhydroxylamines may be used to stop emulsionpolymerization of vinyl chloride.

However, no examples are given, and no advantage is noted. The referencesuggested that dialkylhydroxylamines have a “non-toxic andnon-discoloring nature”, but this is in reference to use with variousrubbers, and the distinction may be drawn between non-discoloring andstabilization of color; the former suggests non-involvement in colorformation whereas the latter implies an interference in color-producingprocesses.

WO 98151714 discloses the use of ethylhydroxylamine as a shortstoppingagent for free radical polymerization. However, novelty is claimedthrough the allegedly “surprising non-volatility” of ethylhydroxylamine,as well as its low corrosively and water solubility. However thispatent, while claiming use for all free radical polymerizations,discusses only emulsion polymerization of rubbers, and all the examplesaddress comparisons related to such processes.

U.S. Pat. No. 4,749,757 includes the use of DEHA (and otherpolymerization inhibitors) in conjunction with PVA (a suspension agent)to simultaneously increase the density and porosity of PVC bymaintaining a low concentration (5-10 ppm preferred) in the reactor.However, DEHA is not disclosed as a shortstopper for PVC.

In JP 02235912, Kanolo et al describe a “reaction product of DEHA,cyclopentadiene, and pyrogallol” which when applied to reactor wallsprevents the formation of scale. This relates to a known applicationwhich exploits the properties of hydroxylamines as part of a coating toimpart antiscaling properties to the walls of PVC reactors.

U.S. Pat. No. 6,340,729 describes the use of DEHA with selected organicperoxide initiators to improve color and heat stability of the PVCresin. This patent compares the use of DEHA with other commonshortstoppers and discusses that an excess of the shortstopping agent,diethylhydroxylamine will lead to yellowing of the resin.

It is also known in the art to use DEHA as a “kill” agent, to haltrunaway vinyl chloride polymerization. Due to DEHA's excellentsolubility and thus rapid miscibility in water, it is effective inhalting vinyl chloride polymerization when, for example, an unexpectedpower outages or if mechanical issues arise.

In accordance with the present invention, it has been discovered thatcombinations of at least one substituted hydroxylamine shortstopper withtotally or partially hindered phenolic antioxidants provide excellentpolymerization kinetics and a rapid, efficient shortstopping, resultingin high yields of high-quality polymer at low cost and minimal change incolor. The overall cost of PVC production is reduced by using ahydroxylamine and lower concentrations of totally or partially hinderedphenolic antioxidants.

When vinyl chloride resin derived from the described process iscompounded, the thermal stability and color of the product is sometimesfound to be improved over resin which has been made with only asubstituted hydroxylamine shortstopper and no antioxidant.

Another aspect of the invention relates to the process which providesexcellent polymerization kinetics and a rapid, efficient shortstopping,resulting in high yields of high-quality polymer at low cost by the useof combinations of alkyl substituted hydroxylamine shortstopper withtotally or partially hindered phenolic antioxidants and when usingdialkyl peroxydicarbonates, peroxy-tert-alkanoates and diacyl peroxidesinitiators.

In another aspect of the invention for the aqueous suspensionpolymerization of vinyl chloride, alone or as a mixture with anothervinyl monomer, the polymerization initiator comprises at least onecompound chosen from dialkyl peroxydicarbonates, peroxy-tert-alkanoatesand diacyl peroxides and use is made, as agent for halting thepolymerization, of a mono- or dialkylhydroxylamine, each alkyl radicalof which comprises from 1 to 4 carbon atoms. The resins thus obtainedexhibit excellent whiteness.

It has now been found that the combination of an initiating systemcomprising at least one compound chosen from dialkyl peroxydicarbonates,peroxy-tert-alkanoates and diacyl peroxides and of a polymerizationshort-stopper composed of a mono- or di-alkyl N substitutedhydroxylamine and one or more totally or partially hindered phenolicantioxidants makes it possible not only to efficiently stop thepolymerization but also to obtain, at the same time, a PVC or copolymerresin resulting in materials exhibiting excellent heat stability orwhiteness. Furthermore, in comparison with conventional short-stoppers,mono- and dialkyl substituted hydroxylamines exhibit the advantage ofbeing instantaneously dilutable in water at the working concentrationswithout the addition of stabilizer or flammable solvent such asmethanol.

The expression totally or partially hindered phenolic antioxidants asused in this context has the meaning as generally accepted by thoseskilled in the art, i.e. phenolic molecules involving the proximity ofadjacent groups to the phenolic hydroxyl which are large and/or bulkyand tend to hinder the reactivity of the phenolic hydroxyl group (hinderthe phenolic group from exerting its influence as an antioxidant andform R—O. free radicals). The reasoning behind this is that the largeadjacent groups to the hydroxyl group:

1) prevent the formation of the free radical: R—O—H→R—O.+H., and/or2) if the free radical does form on the hindered phenolic compound,R—O., the peroxide free radical, also a large molecule, used to initiatethe polymerization may be too large itself to be able to react with thehindered phenolic free radical due to the adjacent large bulky groups.If the peroxide free radical are not ‘neutralized’ or destroyed by thehindered phenolic free radical, they are still too active in thesuspension (or even in the resin if occluded during the drying step)leading to dehydrochlorination of PVC and eventual yellowing of theresin.

Therefore, the only way to compensate for the inability of the partiallyor totally hindred phenolic molecules, in the absence of ahydroxylamine, is to ‘overdose’ the PVC reactor to ensure there issufficient concentration of the phenolic compound to destroy allresidual organic peroxide initiator molecules. It is common practice ifusing a partially or totally hindered phenolic antioxidant alone to useapproximately 300-750 ppm. Using these high concentrations, to ensuretotal destruction of the peroxide free radical, leads to higherproduction costs.

In addition, using only an antioxidant may never lead to completetermination of the polymerization reaction leading to variability in thequality of the PVC resin.

A subject-matter of the invention is thus a process for the aqueoussuspension polymerization of vinyl chloride, alone or as a mixture withless than 50% of another vinyl monomer, in the presence of apolymerization initiator comprising at least one compound chosen fromdialkyl peroxydicarbonates, peroxy-tert-alkanoates and diacyl peroxides,characterized in that the polymerization formulation contains at leastone or more totally or partially hindered phenolic antioxidants, and inthat the polymerization reaction is halted or shortstopped using apolymerization regulating agent (or short-stopper) comprising mono- ordi alkyl substituted N hydroxylamine,

in which each alkyl radical comprises from 1 to 4 carbon atoms, in theamount of 0.0005 to 0.1 parts by weight per 100 parts by weight ofmonomers.

The stated combination of at least one mono- or di alkyl substitutedN-hydroxylamine along with a totally or partially hindered phenolicantioxidant, according to the invention, provides very effectivepolymerization regulating agents with a surprising synergetic action ofthe specific hydroxylamines and the specific phenolic antioxidant.

A further subject matter of the invention is also a polymerizationregulating agent comprising the stated synergetic combination of atleast one such mono- or di alkyl substituted N hydroxylamine along witha totally or partially hindered phenolic antioxidant.

The oil-soluble initiating system generally used is composed of one ormore radical-generating compounds which trigger the polymerization ofthe monomer component. These radicals generally result from the thermaldecomposition of diacyl peroxides, or dialkyl peroxydicarbonates or ofperoxy-teri-alkanoates. It is industrial practice to express the amountof initiator(s) introduced into the reaction mixture by the overallcontent of active oxygen capable of being released by the initiatingsystem. The total amounts of active oxygen generally used are between0.0005 and 0.01 parts by weight, preferably between 0.0015 and 0.005parts by weight, per 100 parts by weight of monomer component. It isalso possible to use a mixture of peroxide initiators each havingdifferent half-lives for a given temperature, the proportion of one withrespect to the other can range from 1 to 99% by weight, preferably from10 to 90%. At an identical temperature, the greater the concentration ofthe initiator(s), the faster the polymerization kinetics. Similarly, fora given polymerization time, the higher the reaction to temperature, thefaster the polymerization kinetics.

The commercial process of VCM polymerization is typically done in abatch mode and it is generally desirable to stop the polymerizationafter having reached a predetermined degree of VCM conversion, so as toobtain a stable and uniform polymer. Typically conversions is about 60%to 85%.

In dialkyl peroxydicarbonates, each alkyl radical can comprise from 1 to16 carbon atoms and can be linear, branched or cyclic. Mention may bemade, as non-limiting examples of such dialkyl peroxydicarbonates, ofdiethyl, diisopropyl, di-n-propyl, dibutyl, dicetyl, dimyristyl,di(4-tert-butylcyclohexyl) or di(2-ethylhexyl) peroxydicarbonates.Preference is given to peroxydicarbonates in which each alkyl radicalcomprises from 6 to 16 carbon atoms and more particularly todi(2-ethylhexyl)peroxydicarbonate.

The dialkyl peroxydicarbonates used according to the invention areclassified in the family of rapid initiators. They generally have ahalf-life of 1 hour at approximately 0.67° C. and can thus be used forvinyl chloride polymerization temperatures of between 50 and 70° C.

It is also possible to use, as non-limiting examples of very rapidinitiators from the family of the peroxy-tertalkanoates, of1,1-dimethyl-3-hydroxybutyl peroxyneodecanoate,curry]peroxyneodecanoate, 1,1,3,3tetramethylbutyl peroxyneodecanoate and1,3-di(2neodecanoylperoxyisopropyl)benzene. The very rapidperoxy-tert-alkanoates generally have a half-life of 1 hour atapproximately 53-61° C.

The N-substituted hydroxylamines have the following structure formula:

HO—N—R¹R²

wherein R¹ and R² may be the same or different, and are selected from Hand C₁-C₁₂ hydrocarbons, where each hydrocarbon chain may be branched,unsaturated, or have hydrogen substituted with functional groupsselected from —OH, —SO, benzyl, amino, mercapto, keto, carboxyl, orwhere R¹ and R² may form together a cyclic structure (such as in ispiperidinyloxy compounds), with the proviso that at least one of R¹ andR² is different from H.

The substituted hydroxylamine used according to the invention aspolymerization short-stopper is introduced at between 60 and 90% ofconversion by mass, preferably between 65 and 80%, from the time whenthe pressure is seen to drop in the reactor. The amount of mono- ordialkylhydroxylamine to be used can range from 0.0005 to 0.1 parts byweight and is preferably between 0.001 and 0.05 parts by weight per 100parts by weight of monomer component.

The polymerization short-stopper according to the invention ispreferably chosen from dialkylhydroxylamines, the more particularpreferred dialkylhydroxylamine being N,N-diethylhydroxylamine, due toits water solubility, high efficiency, and commercial availability.

The polymers which may be made by the process of this invention includebut are not limited to polyvinyl chloride, so polyvinylidene fluoride,polyvinylfluoride, and PTFE.

The term “aqueous suspension polymerization” is understood to mean apolymerization carried out in the presence of at least one oil-solubleinitiator, the monomer component (vinyl chloride, alone or as a mixturewith another vinyl's monomer) being dispersed by mechanical means in anaqueous medium comprising at least one suspending agent.

The proportion of vinyl chloride in the monomer component is at least50% by weight, preferably greater than 80%. The vinyl monomers which canbe copolymerized in an aqueous suspension with vinyl chloride are wellknown and mention may be made, as non-limiting examples, of vinylesters, such as vinyl acetate, vinylidene halides, such as vinylidenechloride and vinylidene fluoride, acrylic esters, such as butylacrylate, and methacrylic esters, such as methyl methacrylate.

Dispersing or suspending agents generally used in suspensionpolymerization are known protective colloids, for example water-solublepolymers, such as polyvinyl alcohols, polyethylene oxides, water-solublecellulose derivatives, such as so methylcellulose, polyvinylpyrolidone,gelatin and vinyl acetate/maleic anhydride copolymers. These suspendingagents can be used alone or in the form of mixtures in amounts generallyof between 0.01 and 0.5 parts by weight, preferably between 0.04 and 0.2parts by weight, per 100 parts by weight of monomer component.

A system for buffering the pH of the aqueous medium may be used ifdesired by the PVC producer. For example, the pH of the aqueous mediumis about 6-7 at the start of the reaction but may drop to as low as 3.5due to the production of hydrochloric acid. It is preferred, but notnecessary in the scope of this invention to buffer the aqueoussuspension. Typical buffering components include but are not limited tothose containing, carbonate or bicarbonate, phosphates or citrates. Thebuffering pH range is between 5 to 8 and preferably between 5.5 to 7.5.

According to the present invention, an antioxidant is added to thepolymerization medium, either at the start of the reaction or at thedesired conversion. The antioxidant may also be fed slowly andcontinually into the PVC reactor during the course of the polymerizationreaction. The antioxidants are chose such that they contain a partiallyof totally hindered phenolic group. Representative antioxidants include,but are not limited to, butylated hydroxyanisole, butylatedhydroxytoluene, Ciba's Irganox 1076, Ciba's Irganox 245, SchenectadyChemical's Isonox 132 (2,6-di-tert-butyl-4-sec-butylphenol). The amountof the antioxidant can vary from 10 to 1000 ppm and more preferably from25 to 300 ppm.

The aqueous suspension polymerizations of vinyl chloride or of a monomercomponent based on vinyl chloride are generally carried out between 45and 80° C., preferably between 50 and 70° C., which makes possible avery wide use of various peroxide initiators. However, when the chosenpolymerization temperature is not very high (between 30 to and 50° C.),it may prove useful to employ a combination of initiators havingdifferent half-lives at the chosen temperatures, for example comprisinga dialkyl peroxydicarbonate and an initiator from the family of the veryrapid peroxy-tert-alkanoates, or a combination of initiators from thefamily of the peroxy-tert-alkanoates comprising a rapidperoxy-tert-alkanoate and a very rapid peroxy-tert-alkanoate.

When the chosen polymerization temperature is slightly higher (between55 and 65° C.), it may prove useful to employ a combination ofinitiators having different half-lives at the chosen temperatures, forexample comprising a dialkyl peroxydicarbonate and an initiator from thefamily of the rapid peroxy-tert-dialkanoates, or a combination of rapidperoxy-tert-alkanoates.

The process according to the invention can be carried out in a way knownper se consisting, for example, in dissolving a protective colloid in anaqueous medium or a monomer component in dispersing the oil-solublepolymerization peroxide initiator in the aqueous medium or in dissolvingit in the monomer component, and optionally in dissolving a system forbuffering the pH of the aqueous medium. The traces of oxygen arcremoved, so as to have a residual content of oxygen dissolved in thewater of between 0.0005 and 0.05 parts by weight, preferably between0.001 and 0.02 parts by weight, per 100 parts by weight of water. Themonomer component is subsequently introduced into the reactor and thenthe reaction mixture is stirred and brought to a temperature of between45 and 80° C., preferably between 50 and 70° C.

The polymerization is brought to an end by depletion of the liquidmonomer phase and this is reflected by a modification in the monomerliquid/vapor equilibrium and a fall in pressure is observed. At thebeginning of the fall in pressure, the conversion by mass of monomer isin the region of 65-85%.

At the end of the desired conversion, the showstopper is injected intoto reactor to destroy or make inactive any residual peroxide initiatormolecules.

Once the polymerization is complete, the polymer formed is separatedfrom the aqueous medium and then it is drained and dried. It generallyexists in the form of particles with a particle size of the order of 80to 250 micrometers.

In a preferred embodiment of the present invention, vinyl chloride ispolymerized in a suspension such as is well known to those skilled inthe art, using an amount of peroxydicarbonate initiator (or mixture ofinitiators including peroxydicarbonate and a “fast” perester) optimal tothe conditions and reactor, and the suspension is shortstopped s by acalculated amount of alkylhydroxylamine, based on an empiricalrelationship, during pressure drop.

In a more preferred embodiment the peroxide used at higher processingtemperatures is di-2-ethylhexylperoxydicarbonate, the alkylhydroxylamineis N,N-diethylhydroxylamine (DEHA) and the phenolic portion of theantioxidant is totally or partially hindered.

In the present invention we have found that both DEHA and a phenolicantioxidant provide a superior heat stable resin when compared to thoseresins using only a hydroxylamine shortstopper particularly thepolymerization process uses di-2-ethylhexylperoxydicarbonate as one ofthe initiators.

In the method of the present invention, the substituted hydroxylamine isused as a shortstopper at the end of the reaction, and the antioxidantmay be added at the start of the polymerization process or along withthe hydroxylamine shortstopper.

The following examples are illustrative of the invention but are notintended to be exhaustive or to limit the invention to the precise formdisclosed. Many other variations and modifications are possible in lightof the specification and examples.

EXAMPLE 1 Synthesis Method for Producing S-PVC (Suspension Process)

A 2-gallon reactor made by American Reactor Corporation (New Carlisle,Ohio) was used.

The polymerization of VCM was done as follows:

1. Coat inside of reactor with antifoulanta. Rinse reactor and stirrer with water to remove excess antifoulant2. Add 5000 ml water to reactor3. Add primary and secondary dispersants to reactor water4. Add to reactor peroxides: front-end initiator, α-cumylperoxneodecanoate added at 410 ppm. The back-end initiator was[di-2-ethylhexyl peroxydicarbonate] and added at 760 ppm.5. Antioxidant (AO) added here if necessary; AO addition—not used in pHstudy6. Seal reactora. Set stirrer to 400 rpm7. Charge 3632 grams (8 lbs.) VCM into reactor

8. Heat to 58° C.

9. Monitor pressure and temperaturea. Pressure stabilizes ˜8.3 bar (120 psi) and temperature about 58° C.10. Continuously add 7 ml/min water to reactor over 2.5-3.0 hourpolymerization timeframe (˜1150 ml in total)11. When the pressure starts to drop from about 8.3 bar (120 psi) to7.58 bar (110 psi), DEHA (or NaHCO₃) is added to an injection port onreactor.a. Addition of NaHCO₃ done at this step in the pH study only; prior tothe addition of DEHA.b. After the addition of DEHA to the injection port, a pressurizednitrogen cylinder is attached to the same injection port that containsthe DEHA.c. The pressure in the reactor continues to slowly drop and when itreaches 6.8 bar (99 psi; Δ20 psi), the cylinder is charged with 15 bar(220 psi) of N₂ gas.d. An inlet valve connecting the reactor to the N₂ cylinder is openedand the differential in pressure between the N₂ cylinder (15 bar; 220psi) and that in the reactor (6.8 bar; 99 psi) causes the flow of N₂ andthe DEHA into the reactor.e. The valve on the reactor: N₂ cylinder is closed and the N₂ cylinderre-pressurized to 15 bar (220 psi).f. Again, the inlet valve connecting the N₂ cylinder to the reactor isopened and the second N₂ stream enters the reactor—this is done toensure all the DEHA is in the PVC reactor.g. The inlet value is closed and the cylinder disconnected.h. The inlet port is filled with water (˜5 ml), the N₂ cylinderreattached, pressurized and this water is then washed with any remainingDEHA into the reactor.12. At this point in the process, the pressure in the cylinder is stillabout 6.8 bar (99 psi).13. The DEHA (and if necessary for pH adjustment, HCO₃ ⁻) is mixed withthe heated slurry at 400 rpm for approximately 1-2 minutes before goingto VCM recovery.

14. Recovery of VCM

a. Unused VCM from the reactor is removed when the pressure drop is 1.38bar (20 psi) from steady-state. Appropriate reactor values are open todraw out any unused VCM and this is sent to the general VCM recovery inthe plant.

-   i. The pressure within the reactor drops to ambient. A N₂ stream    (0.7 bar; ˜10 psi) is inserted into the reactor and sweeps through    the reactor and PVC slurry.-   ii. The temperature of the steam jacket surrounding the reactor is    set to 90° C. (195° F.) and the temperature of the PVC slurry    reaches about 82° C. (181° F.). This additional heat, N₂ stream and    constant stirring assist in removing unused VCM from the PVC    suspension and water. Heating the slurry to 90° C. also helps to    destroy residual peroxide free radicals. This recovery process takes    one hour.    b. After one hour of N₂ purging, the N₂ stream is removed, heat    removed from the reactor jacket and agitation stopped. The PVC    slurry is immediately removed using a drainage value at the bottom    of the reactor, filtered and bagged. The pH of the contrite water    (water removed via filtration) is measured.

15. PVC (Wet Cake)

a. The wet PVC (about 4000 grams; 3625 grams from VCM plus additionalwater in the wet cake) is taken to the laboratory for drying. Somefraction of the PVC is lost as it sticks to the walls of the reactor(about 10% loss).b. 800 gram fractions of the wet-cake are placed in a drying vessel(large cup) that has a fine mesh screen located at the bottom. Threefractions are dried simultaneously whereby hot 95° C. (202° F.) air isflowing through the resin. The resin continuously mixes the resin in afluidized bed process for 45 minutes. When dried, the resin is removedfrom the drying vessels.c. Typical resin weights after drying are about 2400 grams/batch. Thisrepresents about 65% recovery from the initial weight of the VCM. Lossof PVC resin is seen from: a) residual PVC remaining in the reactor andon the stirrer, b) in the transfer containers.d. The resin is then tested for particle size distribution and heatstability.

EXAMPLE 2 Comparative Example

This example shows the poor termination of S-PVC using DEHA alone.

One potential method to study the effectiveness of the termination ofthe polymerization reaction by DEHA is to monitor the change in pressurewith time at the conclusion of the reaction. As the VCM in the slurry isconsumed during the suspension reaction, more VCM from the headspaceenters the suspension thus decreasing the reactor pressure. Typicalpressure drop (ΔP) is about 1.4 bar (20 psi) over a 25-33 minute (Δt)timeframe leading to a ΔP/Δt of about 0.05 bar/min (0.6-0.8 psi/min).Smaller ΔP/Δt slopes indicate easier reaction termination, lessPVC-polymer or peroxide radicals in the suspension, thus leading toslower than average transfer of VCM from the headspace into the slurry.The lower free radical concentration is likely due to the interactions(termination) of the antioxidants with either the peroxide or PVC freeradicals.

Pressure-time transients were recorded for each of the four runsdetailed in the table below; a typical P-t curve is seen below. Theresults are:

Effects of DEHA/pH Pressure Drop (psi/min) DEHA (ppm) 25 100 pH 3.50.772 0.720 pH 6.8 0.714 0.643

It is seen the pressure drop vary from 0.643 to 0.772 with the fastesttermination at the higher pH and highest DEHA concentration.

EXAMPLE 3 Comparative Example

This example shows the effects of combining DEHA with butylated hydroxytoluene (BHT) as totally hindered phenolic antioxidant (AO). The sameprocess as detailed above was used to produce the S-PVC resin but theBHT was added as seen in the table. The pH of the suspension wasapproximately 3.5.

Effects of BHT Pressure Drop (psi/min) DEHA (ppm) 25 100  50 ppm AO0.424 0.405 250 ppm AO 0.303 0.273

It is seen that the combination of DEHA with the antioxidant results infaster termination,

EXAMPLE 4 Comparative Example

This example shows the termination of S-PVC using a long-chainedsubstituted hindered phenolic antioxidant. Irganox 1076 from CibaCorporation was used along with DEHA. The pH of the suspension wasapproximately 3.5:

Effects of 1076 Pressure Drop (psi/min) DEHA (ppm) 25 100  50 ppm AO0.409 250 ppm AO 0.326 0.268

Even faster termination kinetics were obtained using DEHA with thislong-chained antioxidant.

EXAMPLE 5 Comparative Example

This example shows the termination of S-PVC using a long-chainedsubstituted partially hindered phenolic antioxidant. ADDIOX 1045obtained from American Dispersion (Louisville, Ky.) was used along withDEHA. The pH of the suspension was approximately 3.5:

Effects of 1045 Pressure Drop (psi/min) DEHA (ppm) 25 100  50 ppm AO0.341 0.315 250 ppm AO 0.287 0.250

The small ΔP/Δt slopes using a partially hindered phenol along with DEHAshow indicate rapid termination kinetics.

EXAMPLE 6 Comparative Example

This example shows the relative heat stability of resin produced usingonly DEHA at various pHs

Resin Heat Stability—Brabender Studies

The heat stability of the compounded resin was determined by firstblending the resin as follows: 2000 grams of PVC resin+12 grams T-172(Arkema's Thermolite® 172 is a butyltin mercaptide)−mixed at roomtemperature. After mixed, add 16 grams calcium stearate (15F from FerroCorp.) and 4 grams AC-629 (polyethylene wax) and 25 grams XL-165 (Petrac165 wax from Ferro Corp.). The mixture was blended for approximately 5minutes at 60° C. Finally, 40 grams UFT (filler—aCO₃) is added andblended at 85° C. and this mixture is then added to the Brabender.

The compounded resin was put into a Brabender and mixed at 175° C. butthe temperature within the Brabender was actually 200° C. due toadditional frictional heating (see graph below showing torque andtemperature profiles). Samples were pulled every five minutes (note dropin torque every five minutes as Brabender was stopped to remove sample)and pressed onto a piece of paper.

Data from the Brabender was qualitatively ranked according to color from10 (white) to 7 (yellow) to 5 (brown) to 1 (black). Samples were pulledevery five minutes up to 35 minutes and pressed onto a sheet of paper.Typical times for compounded PVC in an extruder is about 10 minutes. Tobetter quantify the effects of heat stability on resin color, plots ofwhiteness vs. time were made from 0-15 minutes and 0-20 minutes toensure we bracketed the time the PVC resin would see in the extruder.

To compare one sample to another, a “standard” was chosen. Results ofvarious runs from the trial are compared to this standard using thispercent difference formula:

(whiteness-time slope of trial run−whiteness-time slope ofstandard)/whiteness-time slope of standard×100%

A positive percent difference indicates the trial sample had a steeperslope value compared to the standard sample indicating less heatstability for that sample vs. the standard sample. A negative percentdifference indicates the sample from that trial had a smallerwhiteness-time slope compared to the standard sample reflecting betterheat stability versus the standard.

Effects of DEHA with pH

The first heat stability study investigated the effects of slurry pHwith DEHA concentrations (no antioxidant). The pH of the slurrydecreases from about pH 6.8 (make-up water) to about 3.5 due to HClproduction during the polymerization reaction. Some PVC producers bufferthe slurry whereas others use no buffer. [Facilities using nitrite asthe shortstopper cannot buffer the suspension as nitrite is noteffective about a pH ˜4.5].

In calculating the results from the Brabender, it is assumed that the100 ppm DEHA/pH 3.5 sample is a typical standard formulation without anantioxidant according to the state of the art. As mentioned above, anegative slope value reported below indicates the slope of the whitenesstime curve for a given sample is better than the control—better heatstability.

Results from the Brabender plots of the change in compounded PVC color(10=white; 5=yellow and 1=black) during extrusion indicate: 1) thehigher the pH of the slurry and 2) the lower concentration of DEHAallows for better heat stability (whiteness):

Effects of pH (20 min Brabender) DEHA (ppm) 25 100 3.5 −17.86% 0.00% 6.8−28.57% −17.86%

At 100 ppm DEHA, increasing the slurry pH from 3.5 to about 6.8increases the color stability. At constant pH, lowering the DEHAconcentration from 100 to 25 ppm also increases the color stability andthe best result is seen at high pH and low DEHA concentration.

EXAMPLE 7 Comparative Example

This example shows the poor performance of PVC samples produced inExample 6 (using DEHA without an antioxidant) when compared against acommercial-grade PVC resin using an antioxidant (approximately 300 ppm)and shortstopped using a molecule other than DEHA.

Effects of pH (20 min Brabender) DEHA (ppm) 25 100 3.5 +31.44% +57.22%6.8 +12.40% +24.40%

It is seen the slopes of the whiteness vs. time for the samples producedusing DEHA and no antioxidant are much steep than the whiteness vs. timeslope for the commercial-grade resin.

EXAMPLE 8 According to the Invention

This example shows the benefits of using DEHA and BHT as an antioxidantcompared to commercially acceptable PVC resin. PVC was produced at acommercial facility using a standard formulation incorporatingapproximately 300 ppm of an hindered antioxidant and a shortstopperother than DEHA. This is now considered the ‘control’ formulationagainst which results from DEHA and BHT are compared to.

The addition of 50 or 250 ppm BHT (as active material) along with DEHAresults in a much better quality resin compared to the resin producedwithout an AO as seen in Example 6. Again, results are now comparedagainst a commercially acceptable PVC resin. The addition of only 50 ppmADDIOX 1005 (BHT) produced almost similar heat stable resins at 25 and100 ppm DEHA. In fact, as little at 50 ppm BHT as an antioxidant canproduce a commercially acceptable resin.

Effects of BHT (20 min Brabender) DEHA (ppm) 25 100  50 ppm AO 15.00%10.00% 250 ppm AO −30.00% 0.00%

EXAMPLE 9 According to the Invention

This example shows the benefits of using a long-chained aliphaticantioxidant along with DEHA on color stability.

The addition of 50 ppm ADDIOX 1016 to the suspension along with DEHAproduces a heat stable resin that is very similar to the commercialgrade resin that needed 300 ppm of the antioxidant. In fact, at 250 ppmADDIOX 1016 and 100 ppm DEHA, a superior heat stable resin is seen.

Effects of ADDIOX 1016 (Irganox1076) (20 min Brabender) DEHA (ppm) 25100  50 ppm AO 8.00% 4.00% 250 ppm AO 0.00% −28.00%

The use of a long-chained aliphatic hindered phenolic antioxidant canallow for as little as 50 ppm of the antioxidant

EXAMPLE 10 According to the Invention

This example shows the benefits of using a partially hindered phenolalong with DEHA in producing commercially acceptable PVC resins

The use of ADDIOX 1045 (obtained from American Dispersion, Louisville,Ky.) produced the most heat stable resin compared to ADDIOX 1005 orADDIOX 1016. Even at low ADDIOX 1045 concentration, the resin is moreheat stable than the present commercial resin. The resin appears tomaintain heat stability better using less DEHA and the best qualityresin was produced using only 50 ppm 1045 and 25 ppm DEHA. In fact, themost heat stable resin is seen using low concentrations of both DEHA andthe antioxidant.

Effects of 1045 (20 min Brabender) DEHA (ppm) 25 100  50 ppm AO −25.00%0.00% 250 ppm AO −14.29% −7.14%

1. A process for the aqueous suspension polymerization of vinylchloride, alone or as a mixture with less than 50% of another vinylmonomer, in the presence of a polymerization initiator comprising atleast one compound chosen from dialkyl peroxydicarbonates,peroxy-tert-alkanoates and diacyl peroxides, characterized in that useis made of a polymerization regulating agent comprising at least onemono- or di alkyl substituted N hydroxylamine having the formula:HO—N—R¹R² wherein R¹ and R² may be the same or different, and areselected from H and C₁-C₁₂ hydrocarbons, where each hydrocarbon chainmay be branched, unsaturated, or have hydrogen substituted withfunctional groups selected from —OH, —SO, benzyl, amino, mercapto, keto,carboxyl, or where R¹ and R² may form together a cyclic structure, withthe proviso that at least one of R¹ and R² is different from H in theamount of 0.0005 to 0.1 parts by weight per 100 parts by weight ofmonomers, along with a totally or partially hindered phenolicantioxidant.
 2. The process according to claim 1, characterized in thatthe polymerization regulating agent comprises a dialkylhydroxylamine inwhich each alkyl radical comprises from 1 to 4 carbon atoms.
 3. Theprocess according to claim 2, characterized in that the polymerizationregulating agent comprises diethylhydroxylamine
 4. The process accordingto claim 1, characterized in that the polymerization initiator comprisesa dialkyl peroxydicarbonate in which each alkyl radical comprises from 1to 16 carbon atoms.
 5. Process according to claim 1, characterized inthat the antioxidant is chosen from butylated hydroxyanisole, butylatedhydroxytoluene, 2,4-dimethyl-6-sec-hexadecylphenol, octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,2,6-di-tert-butyl-4-sec-butylphenol,3,5-di-t-butyl-4-hydroxy-hydrocinnamic acid C₇-C₉ alkylester andmixtures of 2,4-dimethyl-6-sec-hexadecylphenol and octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate.
 6. Polymerizationregulating agent for use in a process for the aqueous suspensionpolymerization of vinyl chloride, alone or as a mixture with less than50% of another vinyl monomer, using a polymerization initiatorcomprising at least one compound chosen from dialkyl peroxydicarbonates,peroxy-tert-alkanoates and diacyl peroxides, characterized in that saidpolymerization regulating agent comprises at least one mono- or di alkylsubstituted N hydroxylamine having the formula:HO—N—R¹R² wherein R¹ and R² may be the same or different, and areselected from H and Ci-C12 hydrocarbons, where each hydrocarbon chainmay be branched, unsaturated, or have hydrogen substituted withfunctional groups selected from —OH, —SO, benzyl, amino, mercapto, keto,carboxyl, or where R¹ and R² may form together a cyclic structure, withthe proviso that at least one of R¹ and R² is different from H. in theamount of 0.0005 to 0.1 parts by weight per 100 parts by weight ofmonomers, along with a totally or partially hindered phenolicantioxidant.
 7. Polymerization regulating agent according to claim 6,characterized in that the polymerization regulating agent comprises adialkylhydroxylamine in which each alkyl radical comprises from 1 to 4carbon atoms.
 8. Polymerization regulating agent according to claim 7,characterized in that the polymerization regulating agent comprisesdiethylhydroxylamine
 9. Polymerization regulating agent according toclaim 6, characterized in that the antioxidant is chosen from butylatedhydroxyanisole, butylated hydroxytoluene,2,4-dimethyl-6-sec-hexadecylphenol, octadecyl3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate,2,6-di-tert-butyl-4-sec-butylphenol,3,5-di-t-butyl-4-hydroxy-hydrocinnamic acid C₇-C₉ alkylester andmixtures of 2,4-dimethyl-6-sec-hexadecylphenol andoctadecyl-3-(3,5-di-tert-butyl-4hydroxyphenyl)propionate.